Solid detergent composition and process for preparation thereof



United States PatentO SOLID DETERGENT COMPOSITION AND PROCESS FORPREPARATION THEREOF j Dmitry Alexis Shiraefli," New York, N.Y., assignorto General Aniline & Film Corporation, a'corporation of Pelaware g NoDrawing. Application July 10, 1951 I Serial No. 236,089. J j

. Claims. (Cl. 252-152) This invention relates to the preparation ofsolid coherent detergent masses or' cakes containing, as the activedetergent component thereof, a normally liquid surfaceactive polyglycolether. l

The manufacture of cakes from synthetic detergents,

suitable for use in the same manner as a cake of ordinary soap, presentsdifficulties even when the synthetic detergent employed is asolid. Thus,solid organic sulfonates and sulfates having detergent properties, suchas the higher alkyl aryl alkali metal sulfonates, and higher fattyalcohol alkali metal sulfuric ester salts, when compressed to a cake,disintegrate rapidly in' water because Patented Mar. 8, 1960 erably 4 to20 lower allrylene glycol residues. Such detergents are prepared, forexample, by condensation of a lower alkylene oxide, especially ethyleneoxide, in the molecular proportions corresponding to the number ofglycol residues to be introduced in the polyglycol radical,

with the higher alcohol or alkyl phenol selected to form the terminalether radical.

This invention is dlrected to thepreparation of solid coherentcompositions containing a liquid polyglycol l0.

ether detergent of the class described in the preceding paragraph. Whilesome of the aforesaid condensation products are viscous pastes or solidwaxvlike materials, many having the most desirable detergent propertiesin, aqueoussolution, especially those containing 4 to 20 oxyethyleneradicals in the polyglycol chain, are liquids of oily or syrupyconsistency at ordinary temperatures. Typical detergents of this kindare the condensation products of isooctyl or nonyl phenol with 8 to 10mols of ethylene oxide, the product being an isooctylor nonylphenylpolyglycol ether.

It is accordingly an obj stable solid coherent compositions containing arelatively large proportion (e.g. up to about 50%) of the aforesaidliquid polyglycol ether detergent in the formof a solid cake, which canalso be reduced to a granular powder,

. suitablefor household and cosmeticiuse.

of their relatively high solubility and the solubility and crystallinestructure of the inorganic salts (e.g. sodium sulfate) which generallyaccompany them in commercial preparations. When rubbed between the handsinwater, excessive amounts of detergent are removed, causing wasting ofthe active ingredient and excessive defatting action on theskin. s I

However, solid detergents can be mixed with binders and other solids toform solid cakes in which solubility aforesaidtype with water-soluble"salts such as alkali l metal sulfates, chlorides, phosphates orsilicates, or with absorbent colloid powderssuchas kieselguh'r, Floridaearth, or silica gel, to form washing powders. The comthepolyglycolether detergent tends to bleed from the In the development ofthis"inventio'n,'it' was found that on adding a normallyxliquidpolyglycol ether detergent to a fused-hydrate of a Water-soluble salt ofa light metal (i.e., a metal having-an atoin'icnumber notgreaterthan20), which hydrate withstandsfusion without decomposie tion, especiallythe hydrates of'magnesium, aluminum and'calcium nitrates magnesium andcalcium chlorides,

' and sodium acetate, a homogeneous liquidyphase is formed which,on'cooli'ng, does notseparateinto. its components, but remains to allappearances homogeneous, and (depending on the proportion-of hydratedsalt presentjtherein) forms a gelatinous to solid homogeneous tions ofthistype contain 40 to 80%. by weight of liquid 7 solid componentof thepowder, moistening containers,

I and interferingwith satisfactory storage, packagingand marketing ofthe compositions. In practice, satisfactory .compositions'of thistypeare generally obtained only by limiting'the amount ofliquidpiilyglyc'olether detergentto a low proportion'generally .well below 10% of thecomposition; If cakes are prepared by compressing such compositions theyhave poorcoherence, arefsnbject to bleeding of the detergent, andrapidlydisintegrate on contact with water.- r

Outstanding detergent; properties characterizeflmonq ethers ofpoly'glycjols in which the terminal ether-forming group is'ahydrocarbonradical of a higher molecular weight monohydric alcohol,-e.g. of' ahigher aliphatic; or alicyclic alcohol of 8 to 20 carbon atoms, asobtained,

for example, by hydrogenation of the carboxyl groups,

as'such orin theform oi anester, injathe. fatty acids of natural fats orin rosin acids and their hydrogenation and dehydrogenation products; orof g a' monohydric alkyl the'polyglycol ether detergents.

mass at room'temperature (20? to 30 C.) which does not separate into itscomponents on standing. .Composipolyglycol ether detergent. The observedformation. of a homogeneous liquid phase from a fused hydrated .salt

and a liquid. polyglycol ether, whi ch fails to. separate on' cooling,vis especially surprising in view of the fact that .the correspondinganhydrous salts are insoluble in Solid masses prepared n the foregoingmannermay have adequate coherence; hardness" andstability againstbinations thusobtained are mere physical mixtures, and

separation to serve as detergent cakes. However, the salts employed intheir preparation are generally deli- "quescent, and theydetergentcompositions sharej the deliquescent properties of the salts from whichthey are made, and if they are exposed for longer periods of time to amoist atmosphere, they become wet on the surface from absorbed moisture.In addition the rela tively high percentage of polyglycol-etherdetergent contained therein is generally unnecessary and wasteful forordinary use. 1 i jUreahas been. suggested as a cake-forming diluentforsolid anionic detergents. When mixed in fused state with the liquidpolyglycol ethers of higher monohydric alcohols or alkylated phenolsdescribed above and having especially desirable detergent properties,urea fails .to form a homogeneous mixture, and the liquid detergentseparates from the urea on cooling. I V

I have discovered, in accordance with this invention,- that'thehomogeneous. liquids obtained by combining polyglycol ether detergentswith the aforesaid fused hydrated phenolcontaining 5 to 20 carbon atomsin nuclear alkyl groups, the polyglycol chain containing, 4 to401and'prefsalts, when mixed with fused urea, combine therewith in awide range of proportions to yield a homogeneous liquid phase. If theproportion of urea is about 0.610

ect of this invention to produce 1.5'times the weight of the polyglycolether-hydrated salt composition, the resulting liquid solidifies oncooling to a solid coherent mass which is homogeneous to all appearancesI-f larger proportions of urea are added, a

homogeneous liquid phase is formed, and on cooling, a solid is likewiseobtained, but it is no longer homogeneous, being shot through withcharacteristic needlelike 7 crystals of urea.

vThe solid masses obtained by cofusion of 0.6 to 1.5

. parts of urea per part of the aforesaid homogeneous mixtures ofhydrated salts with polyglycol ether detergents are no longerdeliquescent, and can be. used as detergent theory, it is possible thatthe effect of urea in eliminating l deliquescence andproducing a mildalkaline reaction re-' sults from reaction of the urea (and such minoramounts of derivatives thereof formed by the effect of heat duringfusion) with the metal'salt in the presence of atmospheric carbondioxide, on the surface of the cake, to form a urea salt andanon-deliquescent metal. carbonate filmwhich; protects the cake fromabsorption of water.

-This effect is more pronounced in the case of metal nitrates'which,because of the insolubility of urea nitrate, tendtoreact more readilywith urea to liberate the metal oxide for reaction with atmosphericcarbon dioxide on the surface of the, mass.

The solid masses obtained in accordance with this invention can bemarketed in the form of cakes for cosmetic andhousehold use.- Moreover,they can be crushed, if desired, to granular products suitable for usein washing powders, Diluents and builders can be readily added to theproducts in granular form, While it is-possible to incorporate inertimmiscible solids in the fused mixture before cooling, it is desirableto avoid admixture with materials having colloidal propertes, since suchmaterials sometimes interfere with the formation of'solid homogeneousmasses on cooling. I

Detergent cakes in accordance with this invention con sistingof a fuseand solidified mixture of urea, a normally liquid polyglycoletherdetergent, and a hydrated salt,-

are relatively soluble-in water and substantial'amounts are lost ifallowed to remain in contact with water, as in an. undrained soap dish.I have further discovered that by inclusionin the fused mixture of'theother ingredients of- 0.25 to 2.0% by weight of a hydrophilic gumsuch as sodiumcarhoxy methyl cellulose or waxy ethylene oxide polymersor polyvinyl alcohol which swell to form a colloidal solution in water,the resulting fused mixture is homogeneous,- remains homogeneous whencooled, and has a much slower'rate of solution in'wate'r. Thus,

. cxcessivewaste of. the cletergent cakes of this invention by reason oftheir solubility in water canbe largely when fusion'is complete, 10'parts of-isooctylphenyl polyethylene glycol rnonoether, containing 8 to10 ethylene oxide radicals per molecule in the polyglycol ether chain,are added. The mixture is agitated at fusion temperature until ahomogeneous'rnixture is obtained. The latter is allowed to coolatroo'rn" temperature, whereby a white, apparently homogeneous, hardcoherent solid is formed. The resulting mass can be exposed to airwithout deliquescence. On rubbing it between the hands in water, it'dissolves slowly anduniformly without disintegration, affordingexcellent washing action.

On reducing the quantity of urea to about 12 parts, or reducing theamount of hydrated. calcium nitrate to 2.5 parts in this example,solidrcakes' are also obtained. On increasing the amount of. urea.to'about 40 parts, a cake is obtained which is still coherent and solid,but is shot through with needlelike crystalsiof urea.

, Example- 2 Homogeneous fusion mixtures result-upon fusing thefollowing mixtures of hydrated salts withtheis'oo'c'tylphenylpolyethylene. glycol ether of the preceding-example.

L Amount Amount; ,of Poly- .Fusiou' Condition on. Hydrate pts. glycolTemp, Cooling to Ether, (3. 20 6.

pts.

(a) osmomimo. 10; 4o so l5 16' ,EQ 1or5 75'- (d) CHsCO0Na.3H O 10 40;(e) MgClz.6HzO 10 10 so Viscous gel.

Solid.

a Viscous gel. Solid. I

Each of these mixtures yield homogeneous liquids which solidify tocoherent solid cakes whenurea'amounting to 0.6 to 1.5 times the combinedamounts ofthe foregoingingredientsisfusedtherewith; Fusion temglycols"'(Carbowax4000or Carbowax 6000) in the examplesgdu-ring: fusion, asan.inert diluent. jFor exam avoided by inclusion of hydrophilic gum of theaforesaid type in the aforesaid proportions with the other ingredients.

The detergent cakes of this invention have outstanding detergentproperties and are effective not only in soft water, butalso in seawater or hard water.-

The preparation of compositions" in accordance with compositions of theforegoing, example subjected to fusion, homogeneous masses'or cakes areobtained on coolingwhich'dissolve at a much lower rate in water,

and which, when submerged in, excess water fora longer 'period,;-so thatthe; urea, hydrated salt and. polyglycol ether detergentiare dissolved,leave a colloidal skeleton of the gum in the; shape of. the originalcake.

Starch; can alsobe mixed with the compositions ofthe ple, l5v parts ofstarch can be included in composition 2(1)) above, during. or prior to-fusion with urea.

1 Instead of. the isooctylphenohpolyglycol ether of the V Camden-3111and Ca(NO' ,,.4H0, either? hydrate; oramixture' of the two, can heusedaccording" to this invention.

The hydrated salts employed inaccordance-with this invention aresaltsof'light metals (i.e., metals having an atomic number up to ZO),which are-i1'1ertltowardthe,

other components employed therewith at fusion temperatures, and whichmelt without'substantial decomposition of the salt, itself or of the'hydrate, i.e., without separation of a different solid phase on fusion,and without boiling at atmospheric pressure; As'indicated in theexamples, hydrates of aluminum, calcium and magnesium nitrates, orcalcium and magnesium chlorides, and sodium acetate are especiallysuitable for use in the compositions of this invention.

The polyglycollether detergents employed in accordance with thisinvention are the liquid condensation products of ethylene oxide (orother lower alkylene oxides such as propylene oxide) with alkyl phenolssuch as triisopropyl phenol, diamylphenol, isooctylphenol, nonyl phenol,dodecylphenol, and octadecylphenol; with higher fatty alcohols such aslauryl, oleyl or stearyl alcohol or mixtures of alcohols resulting fromhydrogenation of the fatty acids of coconut oils; with rosin alcoholssuch as abietyl, dehydroabietyl and dior tetrahydroabietyl alcohols,such condensation products generally containing 4 to 20 mole, and insome cases up to 40,mols, of alkylene.

oxide per mol of the alcohol or phenol with which condensation iseffected.

Fusion of binary compositions of the hydrated salt with the polyglycolether detergent can be carried out at the fusion temperature of thehydrate, or if desired, at a somewhat higher temperature. about 150 C.can be used, but in general, temperatures from the fusion temperature ofthe hydrate to about 25 C. above said fusion temperature are suitable.In preparing the urea compositions of this invention, temperatures inthe vicinity of the melting point of urea are ad- U vantageouslyemployed, e.g. temperatures from 130 to As indicated above, binarycompositions of the liquid polyglycol-alcohol or -phenol ethers with thehydrated salts contain 40 to 80% by weight of the polyglycol ether, theamount of urea being at, least 0.6 parts, preferably 0.6 to 1.5 parts,per part by Weight of the mixture of the other two ingredients. Thus,the weight ratio of hydrated salt to polyglycol ether ranges from 3:2 to1:4. The preferred range of this weight ratio is 3:2 to 2:3.

The solidifiable mixtures obtained by fusion in accordance with thisinvention can be cast in molds to form cakes suitable for cosmetic andhousehold use. The mixtures can also be solidified in masses and crushedto form granular. washing powders. Granulated or'flaked products can beobtained by spraying the fused liquid mass in a cold atmosphere, orflowing the liquid onto cooled flaking drums.

Variations and modifications, which will be obvious to those skilled inthe art, can be made in the compositions and procedures hereinbeforedescribed without departing from the spirit or scope of the invention.

I claim:

1. A detergent composition comprising a solidified homogeneous fusionmass of a normally liquid polyglycol monoether of a member of the groupconsisting of monohydric aliphatic and alicyclic alcohols of 8 to 20carbon atoms and nuclear alkyl substituted monohydric phenols containingto 20 carbon atoms in their nuclear alkyl groups, in which thepolyglycol radical is a chain of 4 to 40 oxyalkylene radicals of 2 to 3carbon atoms with a hydrate of a water-soluble light metal salt of thegroup consisting of magnesium, aluminum and calcium nitrates, magnesiumand calcium chlorides, and sodium acetate, which is stable at fusiontemperature, and urea, the weight ratio of said liquid polyglycol etherto said hydrated light metal salt ranging from 4:1 to 2:3, and theamount of urea being at least 0.6 part per part by weight of themixture, of said hydrate and said polyglycol ether.

2. A detergent composition comprising a solidified homogeneous fusionmass of a normally liquid polyglycol Temperatures up to solubleglightmetal salt of the group consisting of magnesium, aluminum and calciumnitrates, magnesium and calcium chlorides, and sodium acetate, which isstable at fusion temperature, and urea, the weight ratio ofsaid liquidpolyglycol ether to said hydrated light metal salt ranging from 3:2 to2:3, and the amount of urea being 0.6 to 1.5 parts per part by weight ofthe mixture of said hydrate and said polyglycol ether.

3. A detergent composition comprising a solidified homogeneous fusionmass of a normally liquid polyglycol monoether of a monohydric alkylphenol in which the alkyl groupflcontains 8m 9 carbon atoms and thepolyglycol ether radical is a chain of 8 to 10 oxyethylene groups with afusible hydrate of calcium nitrate which is stable at fusiontemperature, and with urea, the weight ratio of said polyglycol ether tosaid hydrate of calcium nitrate ranging from 3:2 to 2:3, and the amountof urea being'0.6 to 1.5 parts .per part by weight of the mixture ofsaid hydrate and said polyglycol ether.

4. A detergent composition "comprising a solidified homogeneous ,fusionmass of a normally liquid polyglycol monoether of a monohydric alkylphenol in which the alkyl group contains 8 to 9 carbon atoms and inwhich'the polyglycol radical is a chain of 8 to 10 oxyethylene groupswith thetetrahydrate of calcium nitrate and urea, the weight ratio ofsaid liquid polyglycol ether to said hydrated calcium nitrate being 1:1and the amount ofurea being 1.5 times the weight of the mixture of saidhydrated calcium nitrate and said polyglycol ether.

5. A detergent composition comprising a solidified homogeneous fusionmass of a normally liquid polyglycol monoether of a monohydric alkylphenol in which the alkyl group contains 8 to 9 carbon atoms and inwhich the polyglycol radical is a chain of 8 to 10 oxyethylene groupswith the tetrahydrate of calcium nitrate and urea, the weight ratio ofsaid liquid polyglycol ether to said hydrated calcium nitrate being 1:1and the amount of urea being 1.5 times the weight of the mixture of saidhydrated calcium nitrate and said polyglycol ether, said fusion massfurther containing a hydrophilic gum selected from the group consistingof sodium carboxy methyl cellulose, polyvinyl alcohol and hard waxlikepolyethylene glycols, amounting to 0.25 to 2.0% of the combined weightof said polyglycol ether, hydrated salt and urea. v

6. A process for preparing a solid detergentcomposition which comprisesfusing together a normally liquid polyglycol monoether of a member ofthe group consisting of monohydric aliphatic and alicyclic alcohols of8- atoms, with a hydrate of a water-soluble light metal salt of thegroup consisting of magnesium, aluminum and calcium nitrates, magnesiumand calcium chlorides, and sodium acetate, which is stable at fusiontemperature, and urea, the weight ratio of said liquid polyglycol etherto said hydrated light metal salt ranging from 4:1 to 2:3, and theamount of urea being at least 0.6 part per part by weight of the mixtureof said hydrate and said polyglycol ether, to form a homogeneous liquidphase, and cooling said liquid phase to room temperature.

7.- A process for preparing a solid detergent composition whichcomprises fusing together a normally liquid polyglycol monoether of amember of the group con sisting of monohydric aliphatic and alicyclicalcohols of 8 to 20 carbon atoms and nuclear alkyl substituted mono- 7hydric phenols containing to 20 carbon atoms in their nuclear alkylgroups and in which the polyglycol radical is a chain of 4 to 20oxyethylene radicals, with a hydrate of a water-soluble light metal saltof the group consisting of magnesium, aluminum' and calcium nitrates,magnesium and calcium chlorides, and sodium acetate, which is stable atfusion temperature, and urea, the weight ratio.

urea being 0.6 to 1.5 parts per part by weight of the 0 mixture of said'hydrate and said polyglycol ether, to form a homogenous liquid phase,and cooling said liquid phase to room temperature. i

8. A process for preparing a solid detergent composition which comprisesfusing together a normally liquid po ys ic he of a monchydric a kyl p enl in which the a y s oup c ta ns. 8 to 9 car n a oms nd the polyglycolether radical is a chainof .3 to oxyfithylene groups, w th a hydra ofcalcium n trat which is stable at fusion temperature, and with urea, theweight ratio of said polyglycol ether to said hydrate of calcium nitrateranging from 3:2 to 2:3, and'the amount of urea being 0.6 to 1.5 partsper part by weight of the mixture of said hydrate and polyglycol ether,to form a homogeneous liquid phase, and cooling said liquid phase toroom temperature.

9. A process for preparing a solid detergent composition which comprisesfusing together a normally liquid polyglycol monoether of a monohydricalkyl phenol in which the alkyl group contains 8 to 9 carbon'atoms andin which the polyglycol radical is a chain of 8 to 10 my ethylene groupswith tetrahydrate of calcium nitrate and urea, the weight ratio of saidliquid polyglycol ether to said hydrated calcium nitrate being 1:1 andthe amount of urea being 1.5 times the weight of the mixture of saidhydrated calcium nitrate and polyglycol ether, to form a homogeneousliquid phase, and cooling said liquid phase to room temperature,

10. A process for preparing a solid detergent composi tion whichcomprises fusing together a normally liquid polyglycol monoether of a'monohydric alkyl phenol in which the alkyl group contains 8 to 9 carbonatoms and in which the polyglycol radical is a chain of 8 to 10oxyethylene groups with tetrahydrate of calcium nitrate, urea, and ahydrophilic gum of the group consisting of sodium carboxy methylcellulose, polyvinyl alcohol, and hard waxlike polyethylene glycols, theWeight ratio of said liquid polyglycol ether to said hydrated calciumnitrate being 1:1, the amount of urea being 1.5 times the weight of themixture of said hydrated calcium nitrate and polyglycol ether, and theamount of said gum being 0.25 to 2.0% of the combined weight of saidpolyglycol ether, hydrated salt and urea, to form a homogeneous liquidphase, and cooling said liquid phase to room temperature. 7

References Cited in the file of this patent UNITED STATES PATENTS FranceOct. 4, 1950

1. A DETERGENT COMPOSITION COMPRISING A SOLIDIFIED HOMOGENEOUS FUSION MASS OF A NORMALLY LIQUID POLYGLYCOL MONOETHER OF A MEMBER OF THE GROUP CONSISTING OF MONOHYDIRC ALIPHATIC AND ALICYCLIC ALCOHOLS OF 8 TO 20 CARBON ATOMS AND NUCLEAR ALKYL SUBMITTED MONOHYDRIC PHENOLS CONTAINING 5 TO 20 CARBON ATOMS IN THEIR NUCLEAR ALKYL GROUPS, IN WHICH THE POLYCLYCOL RADICAL IS A CHAIN OF 4 TO 40 OXYALKLENE RADICALS OF 2 TO 3 CARBON ATOMS WITH A HYDRATE OF A WATER-SOLUBLE LIGHT METAL SALT OF THE GROUP CONSISTING OF MAGNESIUM, ALUMINUM AND CALCIUM NITRATES, MAGNESIUM AND CALCIUM CHLORIDES, AND SODIUM ACETATE, WHICH IS STABLE AT FUSION TEMPERATURE, AND UREA, THE WEIGHT RATIO OF SAID LIQUID POLYGLYCOL ETHER TO SAID HYDRATED LIGHT METAL SALT RANGING FRM 4:1 TO 2:3, AND THE AMOUNT OF UREA BEING AT LEAST 6.0 PART PER PART BY WEIGHT OF THE MIXTURE OF SAID HYDRATE AND SAID POLYGLYCOL ETHER. 